有机配体对加氢处理催化剂的影响进展

简述了近些年来有机配体对加氢处理催化剂的影响研究情况。添加有机配体可以提高加氢处理催化剂活性,从有机配体对加氢处理催化剂的制备及硫化过程的影响角度对文献的研究结果进行了综述,并对有机配体的作用机理进行了分析讨论。文中总结指出,有机配体与活性金属、载体的作用改变了金属与载体的相互作用,影响了金属组分的分散和硫化,从而有利于高活性CoMoS相的生成。     

制备工艺对Ni系液相醛加氢催化剂活性的影响

分别采用浸渍、沉积、水热浸渍和水热沉积四种方法制备了Ni系液相醛加氢催化剂,并通过XRD、XPS和UV-VIS DRS对催化剂进行表征,考察制备工艺对Ni系液相醛加氢催化剂活性的影响.结果表明,水热沉积法制备的催化剂Ni物种有较高的分散度,具有良好的加氢活性,辛烯醛转化率高达99.5％.     

乙二胺四乙酸对NiMo/Al_2O_3催化剂加氢脱氮性能的影响

以氧化铝为载体,Ni和Mo为金属活性组分,添加不同含量乙二胺四乙酸,采用等体积浸渍法制备系列Ni Mo(x)/Al_2O_3(x为乙二胺四乙酸与Ni物质的量比)重质油加氢处理催化剂,考察乙二胺四乙酸加入量对催化剂加氢脱氮性能的影响,并采用N_2物理吸附-脱附、XRD和HRTEM等对催化剂进行表征。结果表明,乙二胺四乙酸的加入增强了金属组分与氧化铝载体间的相互作用,降低了MoS_2活性相的堆垛层数和片层长度,促进了活性相的分散。乙二胺四乙酸与Ni物质的量比为0.5时,MoS_2活性相堆垛层数和片层长度达到良好的结合,对应的催化剂Ni Mo(0.5)/Al_2O_3具有最优的加氢脱氮性能。     

制备过程中碳对加氢处理催化剂性能的影响

采用γ-Al_2O_3为载体,常规浸渍法制备加氢处理催化剂。在浸渍液中加入丙二醇,经过不同温度进行热处理,得到不同碳含量的催化剂。通过H_2-TPR、TEM、XPS等对催化剂表征,考察不同碳含量对加氢处理催化剂加氢性能的影响。结果表明,经过热处理后,有机助剂转化为碳,碳作为隔离分子存在于活性组分与载体之间,削弱活性组分与载体间相互作用力,使活性组分易于还原,活性组分分散度变大;同时MoS_2片晶层数增多、平均长度缩短,活性中心数目增加。催化剂性能评价结果表明,加氢处理催化剂上含有一定量的碳,有利于提高其加氢活性。     

乙醇胺合成乙二胺催化剂的制备及性能表征

以多孔材料为载体,Ni-Co双活性组分为基料,采用浸渍法制备改性Ni-Co双金属催化剂。研究其在乙醇胺还原合成乙二胺中的应用,选择TiO2为载体,Cu、Re为助剂,通过单因素和正交设计实验确定了催化剂制备的最佳条件为:金属负载量10%,镍/钴比4,助剂含量2%,浸渍溶液pH为8。采用XRD和SEM-EDS技术对催化剂的晶型结构、表面微观形貌和元素含量进行表征。结果表明:Ni以分散的金属态存在,Co以氧化物的形式存在,催化剂表面粗糙,比表面积较大,金属含量适当,催化剂活性较好。     

FCC汽油加氢脱硫催化剂研究进展

介绍了国内外FCC汽油中硫存在形式、加氢脱硫反应原理以及研究进展。通过对加氢脱硫活性相结构和其与催化剂活性关系的分析,对不同加氢脱硫制备方法进行分析,对加氢脱硫催化剂的载体、活性组分、助剂方面加以分析,可知发展高活性、高选择性的催化剂仍是现今研究的热点。     

过渡金属对Pt/SiC催化剂上CO氧化性能的影响

以SiC为载体、Pt为活性组分、过渡金属Fe、Co和Ni为助剂,采用浸渍法制备CO氧化催化剂。考察浸渍方法、助剂及其负载量、空速和催化剂焙烧温度等对Pt/SiC催化剂性能的影响。结果表明,助剂的加入提高了活性组分Pt在载体表面的分散度,并产生一定的相互作用,从而提高了催化剂活性,其中,铁助剂的助催化效果较好。共浸渍法制备的催化剂的催化活性优于分步浸渍法,Pt-Fe/SiC催化剂制备中焙烧温度500 ℃时,催化剂活性较佳,适量Fe助剂的添加能够显著提高Pt/SiC催化剂的活性。     

选择加氢催化剂载体氧化铝的改性及其工业应用(Ⅱ)

采用浸渍法制备稀土元素和／或碱金属改性的氧化铝加氢催化剂载体,考察了助剂稀土和碱金属的加入对氧化铝热稳定性、表面酸度的影响以及改性载体对活性组分Pd分散度的影响。采用BET法测定催化剂的比表面积,吸附一脱附法测试催化剂的表面物性,在工业装置上进行催化剂应用试验。结果表明,加入改性组分的氧化铝载体制成催化剂,其活性、选择性均有较大提高。     

还原胺化合成乙二胺催化剂的制备及表征

选择TiO2为载体,Cu和Re为助剂,采用浸渍法制备改性Ni-Co双金属催化剂,研究其在乙醇胺还原胺化合成乙二胺的应用,通过单2因素和正交设计实验确定催化剂制备的最佳条件:金属负载量10%,镍/钴比4,助剂含量2%,浸渍溶液pH为8。采用XRD和SEM-EDS技术对催化剂的晶型结构、表面微观形貌和元素含量进行表征。结果表明,Ni以分散的金属态存在,Co以氧化物的形式存在,催化剂表面粗糙,比表面积较大,金属含量适当,催化剂活性较好。     

两种制备方法对CuO/SBA-16催化CO活性的影响

采用浸渍法和沉淀沉积法制备了Cu O作为活性组分,惰性材料SBA-16作位载体的Cu O/SBA-16催化剂,通过小角XRD、广角XRD、BET、H2-TPR表征及活性测试,发现高分散的Cu O物种为主要的活性物种,并且沉淀沉积法制备的Cu O/SBA-16催化剂中Cu O物种的分散程度更高,氧化CO的活性更好。     

柠檬酸对Ni-W焦化蜡油加氢处理催化剂性能的影响

以含改性HY分子筛的TiO₂-SiO₂复合氧化物为载体,以Ni、W为活性金属组分,采用等体积溶液浸渍法制得了焦化蜡油加氢处理催化剂,考察了浸渍液中加入柠檬酸对催化剂性质及加氢精制性能的影响。BET、FT-IR、XRD、UV-Vis DRS和TG-DSC等表征结果表明,柠檬酸与金属组分间的络合作用提高了金属活性组分的分散度,改变了金属组分的存在状态,促进了单一形式的聚钨酸盐和高活性的六配位八面体Ni物种的形成。柠檬酸改性的Ni-W系催化剂对焦化蜡油的加氢精制性能明显改善,尤其是加氢脱氮性能得以大幅度提高。     

A new and direct preparation method of iron-based bimodal catalyst and its application in Fischer–Tropsch synthesis

A bimodal iron-based catalyst was prepared by a new one-step impregnation method. The active components were used as the “brick” to directly build the small pores inside the large pores of support, which was quite different from the previous bimodal catalysts that were prepared once more on a bimodal support. Comparing with the unimodal catalysts and conventional co-precipitated catalyst, the prepared bimodal catalyst exhibited excellent activity in Fischer–Tropsch synthesis due to the improved active metal dispersion and fastened diffusion efficiency. This preparation method is much simpler than the previous methods and can be extended to prepare various bimodal catalysts with different chemical compositions.     

Steam reforming of bio-oil derived small organics over the Ni/Al2O3 catalyst prepared by an impregnation–reduction method

An impregnation–reduction method has been developed in this study to prepare the Ni/Al₂O₃ catalyst for steam reforming of bio-oil model compounds for hydrogen production. This method can alleviate the interactions between nickel species and an alumina carrier and promote metal dispersion and utilization of the nickel species, achieving a highly active, selective and stable reforming catalyst. Moreover, this method is very simple and fast. Only the impregnation and reduction steps are involved and the catalyst can be prepared in situ. In addition, coke formation in steam reforming is not uniform on a catalyst bed. Coking in the topmost catalyst layer is much more serious.     

Highly dispersed NiW/γ-Al2O3 catalyst prepared by hydrothermal deposition method

This article describes a novel hydrothermal deposition method for preparing highly dispersed NiW/γ-Al₂O₃ catalysts and demonstrates its advantages over the conventional impregnation method. Via the hydrothermal precipitation reactions between sodium tungstate and hydrochloric acid and between nickel nitrate and urea, respectively, the active species W and Ni were deposited on γ-Al₂O₃. In the hydrothermal deposition of WO₃, a surfactant hexadecyltrimethyl ammonium bromide (CTAB) was used to prevent the aggregation of WO₃. The characterization results obtained by means of X-ray photoelectron spectroscopy (XPS), N₂ adsorption and high-resolution transmission electron microscopy (HRTEM) measurements showed that compared with the catalyst prepared by the conventional impregnation method, the catalyst with the same metal contents prepared by the hydrothermal deposition had much higher W and Ni dispersion, higher specific surface area, larger pore volume, the significantly decreased slab length and slightly increased stacking degree of sulfided W species, leading to the significantly enhanced dibenzothiophene (DBT) hydrodesulfurization (HDS) activity. The DBT HDS assessment results also revealed that the catalyst containing 17.7 wt% WO₃ and 2.4 wt% NiO prepared by the hydrothermal deposition method had the similar DBT HDS activity as a commercial NiW/γ-Al₂O₃ catalyst containing 23 wt% WO₃ and 2.6 wt% NiO, resulting in the greatly decreased amount of active metals for achieving the same HDS activity.     

甲烷二氧化碳催化重整制取合成气的研究进展

近几十年来,甲烷二氧化碳催化重整反应引起了广泛的关注。综述了甲烷二氧化碳催化重整制取合成气的研究进展,介绍了催化剂的活性组分、载体、助催化剂及制备方法的研究现状和它们对催化剂活性和稳定性的影响情况,并对催化剂积炭的形成和消除、重整反应机理进行了讨论和分析。     

我国合成气一步法制低碳烯烃催化剂研究新进展

合成气一步法制低碳烯烃作为优势明显的非石油路线替代技术,至今仍未工业化的一个关键问题即催化剂的选择性较差。本文介绍了近十年来关于该催化剂的研究进展,分析了活性组分、助剂、载体及制备工艺分别对催化剂结构与性能的影响,认为Fe系与Co系是最有应用前景的催化剂,碱金属、碱土金属、过渡金属、稀土金属及非金属在调变催化剂酸碱性与电性上各自表现出不同的正作用,抑制了低碳烯烃的二次加氢副反应。分子筛等载体的表面性质与孔道结构可控,方便低碳烯烃从催化剂中扩散移除。浸渍、沉淀、溶胶-凝胶、熔融、水热、微波、超临界、真空干燥等工艺的改进或结合更有利于活性组分的分散和超细颗粒的形成。指出催化剂配合适宜的工艺及反应器才能发挥最大效能,才有可能突破F-T合成中低碳烯烃收率低的ASF规律的限制,实现合成气一步法制低碳烯烃的产业化推广。     

Support effects in the hydrotreatment of model molecules

The support effect on the activity of hydrotreating catalysts using model molecules was analyzed for catalysts supported on TiO₂, SiO₂ and MgO. The results reported in the literature indicate that adequate design of the characteristics of the catalytic support is of great importance in the development of better hydrotreating catalysts. It was shown that by means of an adequate support design it is possible to increase significantly the HDS, HYD and HDN functionalities of hydrotreating catalysts. Semiconducting supports like TiO₂ can improve the HDS and HYD activities by exerting electronic effects on the active phase, helping in this way the formation of sulfur vacancies. Alumina supports modified by SiO₂ can facilitate the sulfidation of the active species, leading to better-promoted type II active sites with increased HDS and HYD catalyst functionalities. The nature of the support affects the sulfidation and dispersion of the catalysts even when chelating agents are used during catalyst preparation.     

Highly Active HDS Catalyst for Producing Ultra-low Sulfur Diesel Fuels

Cosmo Oil Co., Ltd. developed a highly active CoMo HDS catalyst, C-606A, for the production of ultra-low sulfur diesel fuels. This patented preparation method involves impregnation of the support with a solution containing CoCO₃, MoO₃, citric acid, and phosphoric acid, and air-drying without calcination, to provide the high activity HDS catalyst. XPS studies suggested that the addition of citric acid to the impregnation solution during catalyst preparation prevents the sulfidation of Co at low temperature and the uncalcining procedure during catalyst preparation promotes the sulfidation of Mo at low temperature, thereby increasing the formation of the Co–Mo–S structure. The results of the catalytic characterization and the reactivities of the sulfur species and nitrogen species in diesel fuel during the hydrotreating process on C-606A clearly indicate that significant improvements of catalytic activity of the developed catalyst can be achieved by improving the intrinsic activity of the active sites, as well as by increasing the number of Co–Mo–S structure. The commercial operation directly demonstrates the excellent activity and stability of C-606A under industrial operating conditions.     

Preparation,characterization and kinetic behavior of supported copper oxide catalysts on almond shell-based activated carbon for oxidation of toluene in air

Dispersed copper oxide nano-catalysts supported on almond shell-based activated carbon were prepared for catalytic oxidation of toluene in air. The response surface methodology was used to express the catalyst removal efficiency in terms of catalyst metal loading and calcination temperature. Catalyst activity increased with both increasing calcination temperature and metal loading. Calcination temperature had a significant effect on the catalyst activity only at high metal loadings. Two different catalyst preparation methods were employed to investigate the effect of impregnation technique on the deposition–precipitation method. Well-dispersed nano catalysts with higher efficiency towards oxidation of toluene were prepared by the heterogeneous deposition–precipitation (HDP) as compared with the combined impregnation and deposition–precipitation method. The support and catalyst properties were determined by X-ray diffraction, Transmission electron microscopy, field-emission scanning electron microscope, Boehm test, Brunauer–Emmett–Teller surface area measurements, and energy-dispersive X-ray spectroscopy. Characterization analyses and reaction experiments indicated the antonym effect of impregnation method on the deposition–precipitation method for catalyst preparation. Two types of crystallite (large and small) were formed on the support as a consequence of using the combined catalyst preparation method. Kinetic models were proposed for oxidation of toluene using copper oxide catalysts prepared by the HDP method. The kinetic study indicated that an Eley–Rideal mechanism could adequately describe the kinetic behavior of toluene oxidation.